CN104324730A - Catalyst for calcium carbide furnace gas deoxidation and preparation method thereof - Google Patents
Catalyst for calcium carbide furnace gas deoxidation and preparation method thereof Download PDFInfo
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- CN104324730A CN104324730A CN201410543015.2A CN201410543015A CN104324730A CN 104324730 A CN104324730 A CN 104324730A CN 201410543015 A CN201410543015 A CN 201410543015A CN 104324730 A CN104324730 A CN 104324730A
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- catalyst
- calcium carbide
- platinum
- active component
- deoxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 45
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002803 maceration Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 230000001147 anti-toxic effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 238000006356 dehydrogenation reaction Methods 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006424 Flood reaction Methods 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229910002535 CuZn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000079 presaturation Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a catalyst for calcium carbide furnace gas deoxidation, the catalyst comprises active components, an active assistant agent and a carrier, the active components comprise Cu and Pt, on the basis of oxide, the weight percentage of the active component Cu is 10-50%, the weight percentage of the active component Pt is 0.1-3%, the active assistant agent comprises one or more of Zn, Fe and Al, on the basis of oxide, the weight percentage of the active assistant agent is 1-30%; and the rest is the carrier. The catalyst adopts Pt and Cu as the active components, and has certain antitoxic properties, high deoxidation activity, good stability and low deoxidation temperature, oxygen in the calcium carbide furnace gas can be removed to lower than 1.0ppm (1 *10 <-6> (V / V)), the preparation method is simple, and the catalyst is suitable for large-scale industrial application. The invention also discloses a preparation method of the catalyst.
Description
Technical field
The present invention relates to the deoxidizing purification process of calcium carbide furnace gas, particularly a kind of catalyst for calcium carbide furnace gas deoxidation, with and preparation method thereof.
Background technology
Calcium carbide is a kind of important basic chemical industry raw material, and chemical name is calcium carbide, and calcium carbide and water react obtained acetylene, and acetylene is the base stock of synthetic organic chemical manufacturing industry, can synthesize a series of organic compound, for industry, agricultural, medicine are supplied raw materials.
In calcium carbide production, carbon material and lime react, and generate calcium carbide (calcium carbide) and CO.Calcium carbide industry main production plant is furnace of calcium carbide, is divided into internal combustion type furnace of calcium carbide and closed type calcium carbide furnace two class.Internal combustion type furnace of calcium carbide is compared with closed type calcium carbide furnace, and energy consumption of unit product is higher, and waste discharge amount is comparatively large, 11th Five-Year " period has been forced to eliminate.At present, the closed type calcium carbide furnace production technology that China has independent intellectual property right is ripe, and has had the application of certain scale.Carry out the ripe of internal combustion type furnace of calcium carbide transformation closed type calcium carbide furnace comprehensively.
Closed type calcium carbide furnace, by installing bell additional, makes furnace of calcium carbide airtight, has completely cut off extraneous air, and the CO gas air-extractor produced by calcium carbide production process is extracted out and utilized.Auto feed pipe is equipped with bell simultaneously.Closed type calcium carbide furnace is also supporting the devices such as electrode control system, flue gas cleaning, gas burning lime kiln.Compared with the first two type of furnace, closed type calcium carbide furnace due on boiler face without combustion flame, carbon material combustible loss and heat-energy losses little, simultaneously calcium carbide furnace gas can be used as after purified treatment gas burning lime kiln fuel or as organic synthesis raw material, accomplish that resource makes full use of; Do not have flame and dust around furnace of calcium carbide, boiler face device temperature is lower, improves work, safe operating conditions; Furnace charge is fed in raw material by auto feed pipe, and press the operations such as electrode and adopt Automated condtrol, mechanization degree is high, and equipment runs reliably safer.
Usually form from sealed furnace calcium carbide furnace gas out: CO 75 ~ 85%, H
25 ~ 15%, CO
21.5 ~ 5%, O
20.5 ~ 3%, CH
41 ~ 2%, N
21 ~ 10%, tar 1 ~ 2%, H
2s < 600mg/m
3, COS < 300mg/m
3, CS
2> 3000mg/m
3, thiophene < 1mg/m
3, mercaptan < 300mg/m
3, PH
3< 300mg/m
3, NH
3< 30mg/m
3, NOx < 200mg/m
3, separately containing AsH
3, the impurity such as HCN.
Chinese Patent Application No. be 201110196752.6 patent application disclose a kind of calcium carbide furnace gas purification concentrate CO method: by calcium carbide furnace gas dedusting, cooling decoking, Temp .-changing adsorption preliminary clearning, supercharging, sulfur-resistant catalytic deoxidization, hydrolysis desulfurization, depickling gas, dearsenification, fine de-sulfur, smart deoxidation, drying, pressure-changed adsorption concentrating CO.
In above-mentioned cleaning project, the catalyst for CO deoxidation of the domestic current bibliographical information of deoxidation step mainly comprises two large classes, and one is with the catalyst of noble metal for main active component, comprises Pd/Al
2o
3(active carbon), PdMnO/Al
2o
3, PdAu (Ag)/Al
2o
3(TiO
2) etc.; Two is non-precious metal catalysts, mainly contains CuMnCo/ active carbon, CuZn/Al
2o
3(active carbon), CuOMnO+ auxiliary agent Zn (Ni, Au)/Al
2o
3deng.Noble metal catalyst deoxy activity based on Pt, Pd in these catalyst is high, side reaction is less, but expensive, and serviceability temperature is high, be generally used for removing of micro amount of oxygen, and noble metal catalyst easily forms carbonyls and causes activity decrease in high concentration CO gas.Non-precious metal catalyst is copper, manganese system mainly, this kind of dehydrogenation catalyst is cheap, but reactivity is low, when serviceability temperature is more than 150 DEG C, when unstripped gas oxygen content height, easy temperature runaway causes copper-based catalysts sintering deactivation, and the side reaction of carbon monoxide (comprising disproportionation, methanation etc.) is more serious.And the reducing/regenerating temperature of manganese system dehydrogenation catalyst is higher, energy consumption is large, and bad mechanical strength, easy efflorescence, is unfavorable for that heavy industrialization is applied.
Chinese invention patent CN1220302A discloses one for the synthesis of qi exhaustion VPO catalysts, and it consists of CuMnCo/ active carbon, can carry out degree of depth deoxidation to the synthesis gas being less than 1% oxygen content, and after purification, gas remaining oxygen is less than 1.0ppm.But this catalyst low-temperature activity is poor, during reaction temperature height, cause again the sintering of copper-based catalysts, reduce service life.In addition in high concentration CO gas, during temperature height, CO disproportionated reaction is accelerated, and easily causes catalyst surface carbon deposit, thus causes catalyst life to shorten.
Chinese invention patent CN1227139A discloses a kind of for deoxidation catalyst in high concentration CO, take palladium as main catalytic composition, one of Ag, Au, Cr, V for auxiliary agent obtained.This deoxidier is used for high concentration CO deoxidation, has higher activity and selectivity, good stability and deoxidation precision.But it uses air speed on the low side, and deoxidation treatment amount is little, and use cost is higher.This catalyst preparation process is also very loaded down with trivial details in addition, and carrier needs to carry out the heat treatment of presaturation absorbing high temp with organic oxygen-containing compound, and energy consumption and pollution are very large, are not suitable for industrial large-scale production.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, a kind of catalyst for calcium carbide furnace gas deoxidation is provided, it is the difunctional dehydrogenation catalyst that is active component with noble metal and base metal compounding ingredients, have employed Pt, Cu is active component, overcome with single noble metal as active component reaction temperature is high, poison resistance is low and, shortcoming, the performance complement such as side reaction serious low with base metal active component activity.In addition, present invention also offers the preparation method of described catalyst.
To achieve these goals, the present invention adopts following technical proposals:
For a catalyst for calcium carbide furnace gas deoxidation, be made up of active component, coagent and carrier, it is characterized in that:
Described active component is Cu and Pt, active ingredient copper, and with oxide basis, weight percentage is 10 ~ 50%, and the weight percentage of platinum is 0.1 ~ 3%;
Coagent is one or more in Zn, Fe, Al, and with oxide basis, weight percentage is 1 ~ 30%;
All the other are carrier.
Adopt Pt, Cu to be active component, its performance complement, overcome with single noble metal as active component reaction temperature is high, poison resistance is low and, the shortcoming such as side reaction serious low with base metal active component activity.
Pt is to O
2have stronger adsorption capacity, and the easy CO absorption of Cu forms the Metal carbonyl complex of less stable, Pt-Cu bimetallic active component utilizes it to O
2with the adsorption capacity of CO, greatly CO and O in reacting gas can be increased
2the probability of contact and accelerated reaction, thus improve the activity of catalyst.
Experimental study shows that 1% platinum catalyst is reused in 6 times and had very high reaction conversion ratio and selective.
Described active component Cu be selected from cuprous oxide, copper nitrate, Schweinfurt green or copper sulphate any one; Described active component platinum be selected from platinum sulfide, platinum acetate or platinum nitrate any one.
Described coagent be selected from the nitrate of Zn, Fe, Al, chloride, acetate any one or a few.
Described carrier is one or more in silica, magnesia or zirconia.
A preparation method for the described catalyst for calcium carbide furnace gas deoxidation, carries out in accordance with the following steps:
(1) active component Cu and coagent are dissolved in water, are made into mixed solution;
(2) carrier is added that solution that step (1) prepares carries out mediating, extruded moulding, dry, roasting, obtained catalyst precarsor;
(3) platinum salt is dissolved, make the certain density aqueous solution;
(4), in the platinum salting liquid prepared by the catalyst precarsor prepared immersion step (3), normal temperature dipping 4 ~ 8h, dry, roasting, obtains described catalyst.
A preparation method for the described catalyst for calcium carbide furnace gas deoxidation, carries out in accordance with the following steps:
(1) active component Cu and carrier are mixed in proportion;
(2) by step (1) gained mixture through mediating, extruded moulding, dry, roasting, obtained catalyst precarsor;
(3) platinum salt is dissolved, and make maceration extract with the aqueous solution of the salt of coagent;
(4), in the mixed solution prepared by the catalyst precarsor prepared immersion step (3), normal temperature dipping 4 ~ 8h, dry, roasting, obtains described catalyst.
Described method for preparing catalyst is simple, is applicable to heavy industrialization application.
Described catalyst application in unstripped gas air speed be 5000 ~ 15000h
-1, catalytic deoxidation reaction temperature is 80 ~ 200 DEG C.
Preferably, described catalytic deoxidation reaction temperature is 90 ~ 150 DEG C.
Deoxidation treatment amount is large, and reaction temperature is low, air speed 5000 ~ 15000h
-1under, reaction temperature 90 ~ 150 DEG C can reach very good effect.
The oxygen content of deoxidation post-treatment gas is lower than 1.0ppm.
Compared with prior art, the invention has the beneficial effects as follows:
(1) have employed Pt, Cu is active component, its performance complement, overcomes with single noble metal as active component reaction temperature is high, poison resistance is low and, the shortcoming such as side reaction serious low with base metal active component activity.
(2) deoxidation treatment amount is large, and reaction temperature is low;
(3) good stability, poison resistance is strong, and deoxidation precision is high, oxygen can be taken off to 1.0ppm (1 × 10
-6(v/v)) below.
(4) preparation method is simple, is applicable to heavy industrialization application, without the need to reducing/regenerating after first use activation.
Detailed description of the invention
Below in conjunction with detailed description of the invention, foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should comprise within the scope of the invention.
Embodiment 1
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is made up of (by weight) 30% active component, the coagent of 10% and the carrier of 60%, active component be equivalent to cupric oxide be 27% cuprous oxide and be equivalent to the platinum sulfide that platinum is 3%, coagent is that to be equivalent to iron oxide and zinc oxide content in catalyst be iron chloride and the zinc nitrate of 10%, carrier is silica, and preparation method is as follows:
(1) get cuprous oxide 24.3g, silica 60g mixes;
(2) step (1) gained mixture is mediated, extruded moulding, dry 4h at 100 DEG C, roasting 4 hours at 400 DEG C, obtained catalyst precarsor;
(3) get platinum sulfide 3.49g, iron chloride 14.6g (being equivalent to 6.5g iron oxide), zinc nitrate 8.17g (being equivalent to 3.5g zinc oxide), be mixed with dipping solution after adding deionized water dissolving;
(4) catalyst precarsor prepared is immersed in step (3) mixed solution prepared, floods 8h under normal temperature, dry 4h at 120 DEG C, at 450 DEG C roasting 4h the dehydrogenation catalyst 001 of the implementation case.
Embodiment 2
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment by the active component of (by weight) 40.1%, the coagent of 20% and 39.9% carrier form, active component be equivalent to cupric oxide be 40% Schweinfurt green and be equivalent to the platinum nitrate that platinum is 0.1%, coagent is the aluminium chloride and the zinc chloride composition that are equivalent to aluminium oxide and zinc oxide 20% in catalyst, and carrier is zirconia.
(1) Schweinfurt green 45.5g, aluminium chloride 26.2g (being equivalent to 10g aluminium oxide) is got and zinc chloride 16.8g (being equivalent to 10g zinc oxide) is dissolved in deionized water, wiring solution-forming;
(2) get zirconia 39.9g, add the solution that step (1) configures and mediate, extruded moulding, dry 3h at 120 DEG C, 300 times roastings 5 hours, obtained catalyst precarsor;
(3) get 0.16g platinum nitrate and be mixed with solution;
(4) catalyst precarsor prepared is immersed in step (3) the platinum salting liquid prepared, floods 5h under normal temperature, dry 2h at 120 DEG C, at 300 DEG C roasting 5h the dehydrogenation catalyst 002 of the implementation case.
Embodiment 3
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment by the active component of (by weight) 52.1%, the coagent of 30% and 17.9% carrier form, active component be equivalent to cupric oxide be 50% Schweinfurt green and be equivalent to the platinum sulfide that platinum is 2.1%, coagent is be equivalent to the aluminum acetate of aluminium oxide in catalyst, iron oxide and zinc oxide 30%, ferric acetate and zinc acetate composition, and carrier is silica.
(1) getting Schweinfurt green 113.8g, aluminum acetate 40.0g (being equivalent to 10g aluminium oxide), ferric acetate 45.7g (being equivalent to 10g iron oxide) and zinc acetate 35.9g (being equivalent to 10g zinc oxide) is dissolved in deionized water, wiring solution-forming;
(2) get silica 1 7.9g, add the solution that step (1) configures and mediate, extruded moulding, dry 3h at 120 DEG C, 400 times roastings 4 hours, obtained catalyst precarsor;
(3) get 2.44g platinum sulfide and be mixed with solution;
(4) catalyst precarsor prepared is immersed in step (3) the platinum salting liquid prepared, floods 7h under normal temperature, dry 3h at 100 DEG C, at 400 DEG C roasting 4h the dehydrogenation catalyst 003 of the implementation case.
Embodiment 4
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is made up of (by weight) 12% active component, the coagent of 2% and the carrier of 86%, active component be equivalent to cupric oxide be 10% cuprous oxide and be equivalent to the platinum nitrate that platinum oxide is 2%, coagent is the ferric nitrate being equivalent to catalyst 2%, carrier is zirconia, and preparation method is as follows:
(1) get cuprous oxide 10.8g, zirconia 86g mixes;
(2) step (1) gained mixture is mediated, extruded moulding, dry 3h at 120 DEG C, roasting 3 hours at 400 DEG C, obtained catalyst precarsor;
(3) get platinum nitrate 3.27g, ferric nitrate 6.0g (being equivalent to 2g iron oxide), is mixed with dipping solution after adding deionized water dissolving;
(4) catalyst precarsor prepared is immersed in step (3) mixed solution prepared, floods 6h under normal temperature, dry 4h at 120 DEG C, at 500 DEG C roasting 3h the dehydrogenation catalyst 004 of the implementation case.
Embodiment 5
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is made up of (by weight) 51% active component, the coagent of 1% and the carrier of 48%, active component be equivalent to cupric oxide be 50% copper sulphate and be equivalent to the platinum acetate that platinum oxide is 1%, coagent is the aluminum nitrate of the aluminium oxide being equivalent to catalyst 1%, carrier is magnesia, and preparation method is as follows:
(1) get copper sulphate 100g, magnesia 48g mixes;
(2) step (1) gained mixture is mediated, extruded moulding, dry 3h at 120 DEG C, roasting 3 hours at 500 DEG C, obtained catalyst precarsor;
(3) get platinum acetate 1.61g, aluminum nitrate 4.2g, after adding deionized water dissolving, be mixed with dipping solution;
(4) catalyst precarsor prepared is immersed in step (3) mixed solution prepared, floods 4h under normal temperature, dry 4h at 120 DEG C, at 400 DEG C roasting 4h the dehydrogenation catalyst 005 of the implementation case.
Embodiment 6
The present embodiment is the application of calcium carbide furnace gas dehydrogenation catalyst in EXAMPLE l-5 and the evaluation to catalyst deoxy activity.
Catalyst packing carries out deoxy activity test in fixed bed reactors, and loadings is 50ml.Test procatalyst bed directly passes into unstripped gas at air speed 1000h
-1, activate 6h at temperature 200 DEG C, then directly carry out active testing according to test condition change air speed and temperature, different model catalyst activity test concrete outcome is in Table l.Use raw material calcium carbide furnace gas oxygen content to be 0.5 ~ 3%, hydrogen content is 5 ~ 15%, and carbon monoxide content is 75 ~ 85%, and nitrogen is l ~ 10%, and all the other are carbon dioxide, and unstripped gas air speed is 5000 ~ l5000h
-1, catalytic deoxidation reaction temperature is 80 ~ 200 DEG C.
Table 1 catalyst deoxy activity test result
| Catalyst is numbered | Unstripped gas oxygen content % | Deoxidation temperature DEG C | Unstripped gas air speed h -1 | Tail gas oxygen content ppm |
| 001 | 0.52 | 80 | 5000 | 0.43 |
| 002 | 1.07 | 90 | 10000 | 0.77 |
| 003 | 0.96 | 120 | 15000 | 0.73 |
| 004 | 2.73 | 150 | 10000 | 0.85 |
| 005 | 1.96 | 200 | 8000 | 0.98 |
Claims (3)
1., for a preparation method for the catalyst of calcium carbide furnace gas deoxidation, it is characterized in that carrying out in accordance with the following steps:
(1) active component Cu and carrier are mixed in proportion;
(2) by step (1) gained mixture through mediating, extruded moulding, dry, roasting, obtained catalyst precarsor;
(3) platinum salt is dissolved, and make maceration extract with the aqueous solution of the salt of coagent;
(4) in the mixed solution prepared by the catalyst precarsor prepared immersion step (3), normal temperature dipping 4 ~ 8h, dry, roasting, obtains described catalyst;
Described catalyst is made up of active component, coagent and carrier, and described active component is Cu and Pt, active ingredient copper, and with oxide basis, weight percentage is 10 ~ 50%, and the weight percentage of platinum is 0.1 ~ 3%;
Coagent is one or more in Zn, Fe, Al, and with oxide basis, weight percentage is 1 ~ 30%;
All the other are carrier;
Described active component Cu be selected from cuprous oxide, copper nitrate, Schweinfurt green or copper sulphate any one; Described active component platinum be selected from platinum sulfide, platinum acetate or platinum nitrate any one;
Described carrier is one or more in silica, magnesia or zirconia;
Described coagent be selected from the nitrate of Zn, Fe, Al, chloride, acetate any one or a few.
2. the preparation method of the catalyst for calcium carbide furnace gas deoxidation according to claim 1, is characterized in that: described catalyst application in unstripped gas air speed be 5000 ~ 15000h
-1, catalytic deoxidation reaction temperature is 80 ~ 200 DEG C.
3. the preparation method of the catalyst for calcium carbide furnace gas deoxidation according to claim 2, is characterized in that: described catalytic deoxidation reaction temperature is 90 ~ 150 DEG C.
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| CN112705200A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Anti-carbon monoxide poisoning deoxidation catalyst and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994530A (en) * | 2006-12-08 | 2007-07-11 | 昆明理工大学 | Method for removing hydrogen sulfide and hydrogen cyanide from calcium carbide furnace gas |
| CN101016484A (en) * | 2006-12-29 | 2007-08-15 | 中国天辰化学工程公司 | Method of purifying calcium carbide furnace gas |
| CN102303876A (en) * | 2011-05-24 | 2012-01-04 | 天辰化工有限公司 | Method for mixed burning of natural gas and calcium carbide furnace gas |
| CN102382689A (en) * | 2011-08-09 | 2012-03-21 | 中国天辰工程有限公司 | Positive-pressure dry dust removing and purifying method for calcium carbide furnace gas |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN102703133A (en) * | 2012-05-08 | 2012-10-03 | 鹤壁煤电股份有限公司电石厂 | New technology for recycling coal tar of calcium carbide furnace gas |
| CN102706173A (en) * | 2012-05-08 | 2012-10-03 | 鹤壁煤电股份有限公司电石厂 | New calcium carbid furnace gas waste heat utilization process |
| CN102719280A (en) * | 2012-07-10 | 2012-10-10 | 内蒙古宜化化工有限公司 | Calcium carbide furnace gas purifying method |
-
2012
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994530A (en) * | 2006-12-08 | 2007-07-11 | 昆明理工大学 | Method for removing hydrogen sulfide and hydrogen cyanide from calcium carbide furnace gas |
| CN101016484A (en) * | 2006-12-29 | 2007-08-15 | 中国天辰化学工程公司 | Method of purifying calcium carbide furnace gas |
| CN102303876A (en) * | 2011-05-24 | 2012-01-04 | 天辰化工有限公司 | Method for mixed burning of natural gas and calcium carbide furnace gas |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN102382689A (en) * | 2011-08-09 | 2012-03-21 | 中国天辰工程有限公司 | Positive-pressure dry dust removing and purifying method for calcium carbide furnace gas |
| CN102703133A (en) * | 2012-05-08 | 2012-10-03 | 鹤壁煤电股份有限公司电石厂 | New technology for recycling coal tar of calcium carbide furnace gas |
| CN102706173A (en) * | 2012-05-08 | 2012-10-03 | 鹤壁煤电股份有限公司电石厂 | New calcium carbid furnace gas waste heat utilization process |
| CN102719280A (en) * | 2012-07-10 | 2012-10-10 | 内蒙古宜化化工有限公司 | Calcium carbide furnace gas purifying method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705200A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Anti-carbon monoxide poisoning deoxidation catalyst and preparation method and application thereof |
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